The present invention relates to the N-vinylformamide derivative compounds, to polymers thereof and to the synthesis of N-vinylformamide derivative compounds and polymers thereof.
N-vinylformamide (NVF) is a monomer with potentially useful properties in that it free-radically polymerizes to produce water-soluble poly(N-vinylformamide) (PNVF) and also undergoes controlled radical polymerization using RAFT methodology. Badesso, R. J.; Nordquist, A. F.; Pinschmidt, Jr. R. K.; and Sagl, D. J. “Hydrophilic polymers: performance with Environmental Acceptance”, Glass, E.; Ed.; America Chemical Society, Washington, D.C., 1995, p 489. PNVF is probably the most practical precursor for preparation of poly(vinylamine). In that regard, PNVF is easily hydrolyzed under basic or acidic conditions (see Scheme 1) to form poly(vinylamine).

Copolymers of NVF with monomers such as styrene and methyl methacrylate have been generated and are reported to fit a broad range of commercial applications, including water treatment, coatings and paper manufacture. Pinschmidt, Jr. R. K.; Wasowski, L. A.; Orphanides, G. G.; Yacoub, K. Prog. Org. Coat. 1996, 27, 209; Burkert, H.; Brunnmuler, F.; Beyer, K.; Mkroner, M.; Muller, H. U.S. Pat. No. 4,444,667, 1984; Pinschimdt, Jr, R. K.; Chen, N. Polym. Prepr. 1998, 39, 639; Monech, D.; Hartmann, H.; Freudenberg, E.; Stange, A. U.S. Pat. No. 5,262,008, 1993.
NVF is also a multifunctional molecule. In addition to its C═C double bond for addition reactions or polymerization, NVF has a weakly acidic proton on the nitrogen flanked by the formyl and vinyl groups. NVF can thus act as a nucleophile.
A number of N-vinylformamide derivative monomers have been reported. For example, Kurtz, et al. described a process for preparing N-cyanoethyl-N-vinylformamide by the reaction of acrylonitrile and N-vinylformamide in benzene in the presence of potassium cyanide at room temperature. Kurtz, P.; Disselnkoetter, H. Liebigs Ann. 1972, 69–93, 764. Cramer et al. report a process for making N-methyl-N-vinylformamide by the reaction of methyl iodide and N-vinylformamide in the presence of 50% NaOH at room temperature. Cramer, J.; Dehmer, K.; Jensen, H.; Mitzlaff, M.; Pietsch, H.; Pistorius, R.; Schmidt, E. EP 19225, 1980.
Several additional synthetic routes for making N-vinylformamide derivative monomers have been reported. Pinschmidt, Jr., et al., for example, developed 3-(N-vinylformamido) propionates and 2-methyl-3-(N-vinylformamido)propionates by the Michael addition reaction of N-vinylformamide with acrylic or methacrylic acid esters using basic catalysts such as sodium methoxide, sodium hydride, or butyllithium. U.S. Pat. No. 5,463,110. Those monomers have been used in radical polymerizations or as components in photocurable coatings or crosslinking agents and chain extenders. Sugita et al. disclosed a process for making bifunctional crosslinking reagents such as N,N′-methylenebis(N-vinyl acetamide) including N,N′-methylenebis(N-vinylformamide)) by the reaction of N-vinylacetamide with dibromomethane at the room temperature. JP 03,227,310.
It is very desirable to develop new synthetic routes to existing and novel derivatives or analogs of N-vinylformamide as well as to develop new polymers synthesized from such compounds.